Synthetic resin



Patented Jan. 16, 1940 OFFICE SYNTHETIC RESIN Herman A. Brnson and John W. Eastes, Philadelphia, Pa., minors to The Resinous Productc & Chemical Company, Philadelphia, Pa.

No Drawing. Application April so, 1938,

semi No. 295,242

1o Claims. (omen-e3) This invention relates to new synthetic resins is OK, halogen, or -O--acyl, by interor intra- ,molecular esterification.

and a process for preparing same.

We have found that resins are formed by heating, at esteriflcation temperature, ketonic compounds -which, in the acidic form, have the general formula Hooc-a co-R'-o-A-x wherein R is any divalent aliphatic or aromatic coc o cmcn o-omcniocoom Homologous compounds in which the aromatic group R is substituted by inert atoms or groups such as chlorine and the higher alkyl groups or in which thealkylene group or groups of A contain a greater number of carbon atoms, such as the propylene,-butylene, etc. groups are not as economical as the aforementioned but may be used in place of them.

' Acids'of this t D are obtained by condensing aromatic alkylene ether estersoi organic or inorganic acids' in the presence of Friedel-C ratts type oi condensing agents with anhydrides of organic dicarboxylic acids. Many of these are described in ourcopending application, Serial No. 135,672 filed April 8, 1937, Patent No. 2,132,675.

Essential for the resin formation are the two dissimilar combining groups which, upon the appiication of heat, eliminate water, metal halide,

or volatile acid, etc. depending upon whether X .order'to illustrate this invention, the following examples are given- Example 1.-p chloroethoxyethoxybenzoyl-obenzoic acid (prepared by condensing fi-phenoxyfi-chlorodiethyl ether in the presence of A1013 with phthalic anhydride, and which is a crystalline compound, M. P. 12324 C.) was neutralized with an aqueous 2% solution of sodium hydroxide and the clear solution of the sodium salt thus obtained heated in a sealed tube at 150-200 C. for six hours. A hard, colorless,chloroform-soluble resin was obtained, which separated from the aqueous solution of sodium chloride thus formed. The resin was solublein acetone or ethylene dichloride, but was insoluble in hydrocarbons or alcohol.

A similar resin isobtained by fusing the above dried sodium salt in the absence of solvent at 200 C. for six hours, and subsequently washing out the NaCl.

Example .2.'To a well stirredmixture of 49 3'.

-01 phthalic anhydride, 50 g. AlCia, and 250- cc. .of carbon disulfide, there was gradually add ed 75 g. of p-phenoxyethoxyethyl acetate, CcHaOC2H4OC2H4OCOCH3, and the mixture then heated on the, steam bath until HCl evolution ceased. Upon hydrolysis with cold, dilute hydrochloric acid andremoval of the CS2, a viscous oil was obtained which was purified by dissolving in cold, dilute soda solution, and precipitating the filtered solution with dilute hydrochloric acid. The product separated as a pale yellow, viscous oil which analyzed correctly for a substance having the formulacoon Upon heatingthis substance at 190-220 C. for several hours, acetic acid was evolved and a hardv has the formula and rapidly forms a hard, brittle resin when heated at 165-180 C. for several hours until nooo-omom-ooOo-cmom-o-omomoooom was heated at 185 C. for three hours. A hard,

tough resin was obtained.

In a similar manner, any homologues'of these materials having the aforementioned general formula, may be used in the manner indicated to form resins. present during the internal esterification which forms the resin. Typical modifying agents are other alcohols, acids, or esters, among which may be mentioned rosin, phenolic-formaldehyde condensates, fatty oils of the drying, non-drying, or semi-drying type, or their fatty acids, 'polybasic organic acids, and polyhydric alcohols of all types.

What we claim is: V

1. A resin derived by heating at esterification temperature a member of the group consisting of ketonic acids and their salts, having in their acidic form the formula--- HOOC-Rr-COR'OA--X wherein R is a divalent hydrocarbon group 'having at least two carbon atoms selected from the group consisting of the aliphatic and aromatic series, R is an arylene group, A is a member of the group consisting of alkylene radicals and polyalkylene ether radicals, having at least two carbon atoms in each alirylene group, and X is one of the group consisting of 0H, --O-acyl,

and halogen. i g

2. A resin derived by heating at esterincationtemperature, a compound having the general tormulai wherein R is a divalent hydrocarbon group having at least two carbon atoms and selected from the group consisting of the aliphatic and aromatic series, R is an arylene group, and A is. a member of the group consisting of alkylene radicals and polyalkylene ether radicals, having at least two carbon atoms in each alkylene group.

3. A resin derived by heating at esteriflcation temperature, a compound having the general formula wherein R is a divalent hydrocarbon group having at least two carbon atoms and selected from the group consisting of the aliphatic and aromatic series, B. is an arylene group, and A is a member of the group consisting of alkylene' radicals and polyalkyleneether radicals, having at least two carbon atoms in each alkylene group.

I 4. A resin derived by, heating at esteriflcation temperature a member of the group consisting of ketonic acids and their salts. havingin their acidic form the formula wherein R is a divalent aliphatic hydrocarbon group having at least two carbon atoms, R is an arylene group, A is a polyalkylene ether radical having at least two carbon atoms in each alkylene Various modifying agents may be,

ingoiOI-I, -Oacyl, and halogen.

group, and X is one of the group consisting of OH, -O-acyl, and halogen.

5. A resin derived by heating at esteriflcation temperature a member of the group consisting of ketonic acids and their salts, having in their acidic form the formula- Hooc-Ho-w-o-A-x wherein R is a divalent aromatic hydrocarbon group having at least two carbon atoms, R is an arylene group, A is a polyalkylene ether radical having at least two carbon atoms in each alkylene group, and X is one of the group consisting of 0H, -Oacyl, and halogen.

6. A resin derived by heating at esteritlcation temperature a member of the group consisting of ketonic acids and their salts, having in their acidic form the formulaooOo-cmcnr-o-cmcmocoom coon -'7. A resin derived by'heating at esterincation temperature a member of the group consisting of ketonic acids and their salts, having in their acidic form the formulanooc-omom-ooOo-omom-o-cmcmococm '8. A process for preparing a resin which comprises heating a member of the group consisting of ketonic acids and their salts, having in their acidic form the formulaone o! the group consisting of OH, Q-acyl,'

and halogen.

9. A process for preparing a resin which comprises heating a member 0! the group consisting of ketonic acids and their salts, havingin their acid form the formula? wherein R is a divalent hydrocarbon aliphatic grouphaving at least two carbon atoms, R is an arylene group, A is a. polyaligvlene ether radical having at least two carbon atoms in each alkylene group, and]! is one of. the group consisting 0! OH; O-acyl. andhalogen. I

10. A process ior preparing a resin which com- ;brises heating a member or the group consisting oi ketonic acids and their salts, having in their acidic form the formula- Hooo-4a-c OR'0Ax wherein R is a divalent aromatic hydrocarbon group having at least two carbon atoms, R is an arylene group, A is a polyalkylene ether radical having at least two carbon atoms in each alkylene group, and x is one of the group consist- HERMAQLA. BRUSON. JOHN w. nss'ras. 

